CN1221991A - High specific energy lead-acid battery for electric vehicle - Google Patents

High specific energy lead-acid battery for electric vehicle Download PDF

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Publication number
CN1221991A
CN1221991A CN97119880A CN97119880A CN1221991A CN 1221991 A CN1221991 A CN 1221991A CN 97119880 A CN97119880 A CN 97119880A CN 97119880 A CN97119880 A CN 97119880A CN 1221991 A CN1221991 A CN 1221991A
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surplus
weight
alloy composition
described storage
positive
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CN97119880A
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Inventor
陈有孝
胡庸
胡凤翔
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TAIJI ENERGY CO Ltd DALIAN CITY
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TAIJI ENERGY CO Ltd DALIAN CITY
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Priority to CN97119880A priority Critical patent/CN1221991A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

A lead-acid accumulator with high specific energy for electric car is disclosed. The slab lattice of its positive electrode is made up of Pb-Sb alloy. The active substance for positive electrode is prepared from powdered Pb, PTFE, heterographite and K2SO4. The slab lattice of its negative electrode is made up of rare-earth series Pb-Ca alloy. The active substance for negative electrode is prepared from powdered Pb, BaSO4, sodium lignosulfonate and alpha or beta naphthalene acid. Its advantages are high specific energy of weight up to 50 WH/kg, long service life longer than 1000 times and excellent recharge acceptance power and high-multiplication discharge power.

Description

High specific energy lead-acid battery for electric vehicle
The present invention relates to the storage battery field, particularly a kind of high specific energy lead-acid battery that is used for electric motor car.
Electric motor car is a kind of vehicles of pollution-free, fuel-economizing.And electric motor car the most important thing is that reliable power resources will be arranged.At present, the energy that can offer electric motor car mainly contains: nickel-cadmium cell, nickel-hydrogen cell, lithium ion battery and lead-acid battery.These batteries differ from one another, but battery is guaranteeing reliability, and on the basis of fail safe, the energy size that the per kilogram battery is emitted is the important indicator that is applied to electric motor car.In above-mentioned battery, the gravimetric specific energy of nickel-cadmium cell is 40-45WH/kg, and the energy gravimetric specific energy of totally-enclosed nickel-cadmium cell also will hang down.Because the severe contamination and the cadmium resource of nickel-cadmium cell are less, so battery has been to eliminate kind, it obviously is inappropriate being used for electric motor car.The nickel-Hydrogenized compound secondary cell has its good performance as the substitute products of nickel-cadmium cell, and gravimetric specific energy reaches 50-55WH/kg, but it cost an arm and a leg.For lithium ion battery, its gravimetric specific energy is very high, can reach 70-80WH/kg, the research but its fail safe, reliability, especially high power work performance await, and the price of this battery is more expensive, is impossible so be widely used in the electric motor car of the marketization.And ancient lead-acid battery has lot of advantages, and its application has more been widened in the particularly appearance of full sealed lead-acid battery.But the shortcoming of this safety, the life-span is long, price is low battery maximum is that gravimetric specific energy is low, and present world standard only is 30-36WH/kg.Thereby, can not satisfy the electric motor car instructions for use as the energy of electric motor car.
Have in the prior art a kind of big for overcoming the weight and volume that lead acid accumulator exists, the shortcoming that energy is low, and the high-energy-density sealed maintenance-free lead acid battery electrode plate structure of design, and the fit of positive/negative plate.Its lug places the centre position at pole plate edge, can improve the catchment effect of pole plate, increases the capacity of positive/negative plate; The positive/negative plate level stacks form, can increase the surface area of positive/negative plate greatly, response area is increased, improve the serviceability of battery, but because it is at plate railings of anode and cathode, the both positive and negative polarity active material, aspects such as the composition of electrolyte and combination thereof still are weak, and make the specific energy index of battery can not satisfy the needs of electric motor car.
Purpose of the present invention is intended to the plate railings of anode and cathode to traditional lead acid accumulator, the both positive and negative polarity active material, the composition and the combination thereof of electrolyte improve, and propose a kind of high specific energy lead-acid battery that is suitable for electric vehicle, to overcome weak point of the prior art.
Purpose of the present invention can realize by following proposal.
High specific energy lead-acid battery for electric vehicle comprises housing, is positioned at the pole at grid middle part, is the plate railings of anode and cathode that level stacks, and both positive and negative polarity active material and electrolyte the invention is characterized in:
Said anode plate grid adopts lead alloy material, and its alloying component (weight) is: 0.01-1.2%Sb or Bi, 0.01 2.0%As or Na, 0.01-1.0%Cu or Al, 0.01-2.0%Sn, 0.01-1.0%Ag or Ce or La, surplus Pb.
Said positive active material, adding (a) proportion by the Pb powder is 1.25g/cm 3H 2SO 4Solution, (b) 0.01-2%PTFE, (C) the 0.01-0.5% opposite sex graphite, (d) 0.001-0.05%K 2SO 4Make.
It is the lead-calcium alloy material that said negative electrode grid adopts rare earth, and its alloying component (weight) is: 0.02-0.12%Ca, 0.01-0.8%Sn, 0.01-0.05%Al, 0.01-0.05%Ce, surplus Pb.
Said negative electrode active material, adding (a) proportion by the Pb powder is 1.25g/cm 3H 2SO 4Solution, (b) 0.1-0.3%BaSO 4, (c) 0.1-0.3% sodium lignosulfonate, (d) 0.1-0.3% alpha-or beta-naphthoic acid, (e) 0.01-0.1% diffusion agent N 0Make.
Said electrolyte adopts proportion to be: 1.285g/cm 3H 2SO 4Solution adds by volume that percentage is the phosphoric acid of 0.1-2%, and every liter of electrolyte adds 10-100mgK 2SO 4Preparation.
Below in conjunction with embodiments of the invention, high specific energy lead-acid battery for electric vehicle is described in detail.
High specific energy lead-acid battery for electric vehicle is also by housing, pole, the plate railings of anode and cathode that level stacks, compositions such as both positive and negative polarity active material and electrolyte.Wherein:
The positive grid alloy composition can be 0.01-0.1%Sb or Bi, 0.01-0.8%As or Na, 0.01-0.1%Cu or Al, 0.01-0.3%Sn, 0.01-0.1%Ag or Ce or La, surplus Pb.
The positive grid alloy composition also can be 0.1-0.8%Sb or Bi, 0.8-1.5%As or Na, 0.1-0.5%Cu or Al, 0.3 0.9%Sn, 0.1-0.5%Ag or Ce or La, surplus Pb.
The positive grid alloy composition also can be 0.8-1.2%Sb or Bi, 1.0-2.0%As or Na, 0.5-1.0%Cu or Al, 0.7-2.0%Sn, 0.5-1.0%Ag or Ce or La, surplus Pb.
The negative plate grid alloy composition can be 0.02-0.08%Ca, 0.01-0.3%Sn, 0.01-0.03%Al, 0.03-0.05%Ce, surplus Pb.
The negative plate grid alloy composition also can be 0.08-0.12%Ca, 0.3-0.8%Sn, 0.03-0.05%Al, 0.01-0.03%Ce, surplus Pb.
Concrete prescription can have:
The positive grid alloy composition is: 0.1%Sb, 1.5%As, 0.5%Al, 0.3%Sn, 0.5%La, surplus Pb.
The positive grid alloy composition is: 1.0%Bi, 1.1%Na, 1.0%Cu, 1.0%Sn, 0.8%Ce, surplus Pb.
The negative plate grid alloy composition is: 0.06%Ca, 0.3%Sn, 0.02%Al, 0.04%Ce, surplus Pb.
Negative plate grid alloy composition (weight) is: 0.08%Ca, 0.6%Sn, 0.03%Al, 0.02%Ce, surplus Pb.
In addition, plate railings of anode and cathode, the combination embodiment of both positive and negative polarity active material and electrolyte is shown in please seeing attached list: subordinate list: (unreceipted unit is weight %)
????1??????2??????3??????4??????5
Anode plate grid ????Sb ????Bi ????As ????Na ????Cu ????Al ????Sn ????Ag ????Ce ????La ????Pb 0.05 0.06 1.2 0.1 0.8 2.0 0.8 0.01 1.5 0.1 0.01 0.3 1.0 0.1 0.8 2.0 1.5 0.7 0.1 0.01 1.0 0.01 0.7 0.3 0.1 surplus surplus surplus surplus surplus
Positive active material PTEF opposite sex graphite K 2SO 4 ???0.01????0.3????1.0????1.5????2 ???0.01????0.1????0.2????0.3????0.5 ???0.05????0.04???0.03???0.01???0.001
It is 1.25g/cm that the Pb powder adds proportion 3H 2SO 4
Negative electrode grid ????Ca ????Sn ????Al ????Ce ????Pb 0.02 0.05 0.08 0.10 0.12 0.8 0.5 0.3 0.1 0.01 0.01 0.02 0.03 0.04 0.05 0.05 0.04 0.03 0.02 0.01 surplus surplus surplus surplus is surplus
Negative electrode active material ????BaSO 4Sodium lignosulfonate alpha-or beta-naphthoic acid diffusion agent N 0 ???0.1?????0.2?????0.2????0.2?????0.3 ???0.3?????0.2?????0.2????0.2?????0.1 ???0.1?????0.2?????0.2????0.2?????0.2 ???0.01????0.03????0.05???0.07????0.10
It is 1.25 g/cm that the Pb powder adds proportion 3H 2SO 4
Electrolyte Phosphoric acid (volume %) K 2SO 4(mg/l) ???0.1?????0.5?????1.0????1.5?????2.0 ???100?????60??????40?????30??????10
Employing proportion is 1.285g/cm 3H 2SO 4
When making the 12V100AH Lead Acid Battery Used for Electric Vehicle, select with the technology of the present invention:
Its anode plate grid is used: 0.6%Sb, and 0.12%As, 0.05%Cu, 0.2%Sn, 0.05%Ce, surplus is the alloying component of Pb, is heated to 480 ℃ in market pot, is incubated 30 minutes, casting grid when being warming up to 520 ℃ again.Mold temperature is controlled at 160-180 ℃ during casting.
Its positive active material, adding proportion by the Pb powder is 1.25g/cm 3H 2SO 4Solution, 0.05%PTFE, 0.08% different in nature graphite and 0.005%K 2SO 4, in closing the cream machine, close evenly, close the cream time greater than 35 minutes.This positive active material is applied to the anode plate grid surface after leaving standstill 2 hours.Send into curing room immediately and solidify after invading acid, curing time is about 36 hours.
Its negative electrode grid is used: 0.08%Ca, and 0.3%Sn, 0.03%Al, 0.05%Ce and surplus are the Pb alloying component, melt in market pot, are cast into grid.
Its negative electrode active material, adding proportion by the Pb powder is 1.25g/cm 3H 2SO 4Solution, 0.17%BaSO 4, 0.18% sodium lignosulfonate, 0.2% alpha-or beta-naphthoic acid and 0.05% diffusion agent N 0, in closing the cream machine, close evenly, close the cream time greater than 30 minutes.This negative electrode active material is applied to the negative electrode grid surface after leaving standstill 2 hours.Send into curing room immediately and solidify after invading acid, curing time is about 36 hours.
Then, the positive and negative electrode grid is 1.15g/cm at proportion 3H 2SO 4Change in the solution, the energising amount is 4.2 times of pole plate capacity, and the time of changing into was controlled at 20 hours.
At last, with positive and negative electrode grid assembling accumulator.Dividing plate adopts fibreglass diaphragm.Electrolyte component is: 1.285g/cm 3The H of proportion 2SO 4Solution adds percentage by volume and is 1% phosphoric acid, again by adding 30mgK in every liter of electrolyte 2SO 4Electrolyte is pressed 10g/AH inject battery, carry out the performance test of battery after 6 hours.
Above-mentioned 12V100AH accumulator testing result is as follows:
The JISC8707-92 of Japanese Industrial Standards The battery testing result
0.1CA discharge capacity % 3 circulations 〉=95 The second time 108
0.5CA discharge capacity % ????≥60 ????76
1CA discharge time minute ????≥27 ????36
3CA discharge time minute ????≥4 ????6.8
5CA second discharge time ????≥1?70 ????302
10CA second discharge time ????≥80 ????180
The performance of overcharging % ????≥95 ????1?06
Charge acceptance 2.5 constant voltage charges 10 minutes Electric current 〉=0.24CA ????0.28CA
Shelf characteric % (28 days retention of charge) ????78 ????78.2
Cycle life is inferior ????200 ????500
Confined reaction efficient ????≥90 ????98.2
The float life of overcharging ????≥180 ????360
The present invention is through to plate railings of anode and cathode, and the improvement of both positive and negative polarity active material and electrolyte component and reasonable combination have improved every technical indicator of lead acid accumulator effectively.The wherein wt specific energy can reach 50WH/kg, considerably beyond the world level of 36AH/kg.The designed life of battery, indexs such as the charge acceptance of battery, high rate discharge capability also all surpassed Japanese Industrial Standards and international IEC standard greater than 1000 times.

Claims (10)

1 one kinds of high specific energy lead-acid battery for electric vehicle comprise housing, are positioned at the pole at grid middle part, are the plate railings of anode and cathode that level stacks, and both positive and negative polarity active material and electrolyte the invention is characterized in:
Said anode plate grid adopts lead alloy material, and its alloying component (weight) is: 0.01-1.2%Sb or Bi, 0.01-2.0%As or Na, 0.01-10%Cu or Al, 0.01-2.0%Sn, 0.01-1.0%Ag or Ce or La, surplus Pb;
Said positive active material, adding (a) proportion by the Pb powder is 1.25g/cm 3H 2SO 4Solution, (b) 0.01-2%PTFE, (C) the 0.01-0.5% opposite sex graphite, (d) 0.001-0.05%K 2SO 4Make;
It is the lead-calcium alloy material that said negative electrode grid adopts rare earth, and its alloying component (weight) is: 0.02-0.12%Ca, 0.01-0.8%Sn, 0.01-0.05%Al, 0.01-0.05%Ce, surplus Pb;
Said negative electrode active material, adding (a) proportion by the Pb powder is 1.25g/cm 3H 2SO 4Solution, (b) 0.1-0.3%BaSO 4, (c) 0.1-0.3% sodium lignosulfonate, (d) 0.1-0.3% alpha-or beta-naphthoic acid, (e) 0.01-0.1% diffusion agent N 0Make;
Said electrolyte adopts proportion to be: 1.285g/cm 3H 2SO 4Solution adds by volume that percentage is the phosphoric acid of 0.1-2%, and every liter of electrolyte adds 10-100mgK 2SO 4Preparation.
2 according to the described storage battery of claim 1, it is characterized in that said positive grid alloy composition (weight) is: 0.01-0.1%Sb or Bi, 0.01-0.8%As or Na, 0.01-0.1%Cu or Al, 0.01-0.3%Sn, 0.01-0.1%Ag or Ce or La, surplus Pb.
3 according to the described storage battery of claim 1, it is characterized in that said positive grid alloy composition (weight) is: 0.1-0.8%Sb or Bi, 0.8-1.5%As or Na, 0.1-0.5%Cu or Al, 0.3-0.9%Sn, 0.1-0.5%Ag or Ce or La, surplus Pb.
4 according to the described storage battery of claim 1, it is characterized in that said positive grid alloy composition (weight) is: 0.8-1.2%Sb or Bi, 1.0-2.0%As or Na, 0.5-1.0%Cu or Al, 0.7-2.0%Sn, 0.5-1.0%Ag or Ce or La, surplus Pb.
5 according to claim 1 or 2,3,4 described storage batterys, it is characterized in that said negative plate grid alloy composition (weight) is: 0.02-0.08%Ca, 0.01-0.3%Sn, 0.01-0.03%Al, 0.03-0.05%Ce, surplus Pb.
6 according to claim 1 or 2,3,4 described storage batterys, it is characterized in that said negative plate grid alloy composition (weight) is: 0.08-0.12%Ca, 0.3-0.8%Sn, 0.03-0.05%Al, 0.01-0.03%Ce, surplus Pb.
7 according to the described storage battery of claim 3, it is characterized in that said positive grid alloy composition (weight) is: 0.1%Sb, 1.5%As, 0.5%Al, 0.3%Sn, 0.5%La, surplus Pb.
8 according to the described storage battery of claim 4, it is characterized in that said positive grid alloy composition (weight) is: 1.0%Bi, 1.1%Na, 1.0%Cu, 1.0%Sn, 0.8%Ce, surplus Pb.
9 according to the described storage battery of claim 5, it is characterized in that said negative plate grid alloy composition (weight) is: 0.06%Ca, 0.3%Sn, 0.02%Al, 0.04%Ce, surplus Pb.
10 according to the described storage battery of claim 6, it is characterized in that said negative plate grid alloy composition (weight) is: 0.08%Ca, 0.6%Sn, 0.03%Al, 0.02%Ce, surplus Pb.
CN97119880A 1997-12-31 1997-12-31 High specific energy lead-acid battery for electric vehicle Pending CN1221991A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317789C (en) * 2005-06-24 2007-05-23 沈涛 Valve controlling type sealed lead acid battery with Nano carbon in electrolyte
CN100386457C (en) * 2004-07-14 2008-05-07 新乡市卓威电源有限责任公司 Process for preparing Pb-base mixed rare earth slab lattice alloy
CN101824562A (en) * 2010-04-30 2010-09-08 张天任 Positive grid alloy material for lead-acid storage battery
CN102938473A (en) * 2012-11-11 2013-02-20 骆驼集团华南蓄电池有限公司 Lead-acid storage battery
CN105977549A (en) * 2011-10-18 2016-09-28 日立化成株式会社 Lead storage battery
CN108352579A (en) * 2015-11-17 2018-07-31 株式会社杰士汤浅国际 Lead accumulator and its manufacturing method
CN111659733A (en) * 2020-06-08 2020-09-15 宁夏天元锰材料技术开发有限公司 Electrolytic manganese anode plate grid and manufacturing method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100386457C (en) * 2004-07-14 2008-05-07 新乡市卓威电源有限责任公司 Process for preparing Pb-base mixed rare earth slab lattice alloy
CN1317789C (en) * 2005-06-24 2007-05-23 沈涛 Valve controlling type sealed lead acid battery with Nano carbon in electrolyte
CN101824562A (en) * 2010-04-30 2010-09-08 张天任 Positive grid alloy material for lead-acid storage battery
CN105977549A (en) * 2011-10-18 2016-09-28 日立化成株式会社 Lead storage battery
CN105977549B (en) * 2011-10-18 2019-03-29 日立化成株式会社 Lead storage battery
CN102938473A (en) * 2012-11-11 2013-02-20 骆驼集团华南蓄电池有限公司 Lead-acid storage battery
CN102938473B (en) * 2012-11-11 2015-08-19 骆驼集团华南蓄电池有限公司 Lead acid accumulator
CN108352579A (en) * 2015-11-17 2018-07-31 株式会社杰士汤浅国际 Lead accumulator and its manufacturing method
CN108352579B (en) * 2015-11-17 2021-06-08 株式会社杰士汤浅国际 Lead storage battery and method for manufacturing the same
CN111659733A (en) * 2020-06-08 2020-09-15 宁夏天元锰材料技术开发有限公司 Electrolytic manganese anode plate grid and manufacturing method thereof

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